KR20200118112A - Polyurethane with low emission of organic compounds - Google Patents

Abstract

The present invention relates to (a) a polyisocyanate, (b) a polymer compound having an isocyanate-reactive group, (c) a catalyst, and optionally (d) a blowing agent, (e) a chain extender and/or crosslinking agent, and (f) an auxiliary agent and/or additive. Mixing to provide a reaction mixture, and reacting the reaction mixture to provide polyurethane, wherein the polymer compound (b) is obtained by polycondensation of an acid component and an alcohol component. Polyesterol (b1), the acid component comprises malonic acid and/or derivatives thereof, and the alcohol component comprises an aliphatic dialcohol having 4 to 12 carbon atoms. The invention further relates to polyurethanes obtainable by the method and to use in enclosed spaces.

Description

Polyurethane with low emission of organic compounds

The present invention relates to (a) a polyisocyanate, (b) a polymer compound having an isocyanate-reactive group, (c) a catalyst, and optionally (d) a blowing agent, (e) a chain extender and/or crosslinking agent, and (f) an auxiliary agent and/or additive. Mixing to provide a reaction mixture, and reacting the reaction mixture to provide polyurethane, wherein the polymer compound (b) is obtained by polycondensation of an acid component and an alcohol component. Polyesterol (b1), the acid component comprises malonic acid and/or derivatives thereof, and the alcohol component comprises an aliphatic dialcohol having 4 to 12 carbon atoms. The invention further relates to polyurethanes obtainable by said method and to use in enclosed spaces, for example interiors of vehicles.

Polyurethane is, for example, in the furniture industry, such as a seat cushioning material or a binder for particle boards, as an insulation material in the construction industry, as an insulation material such as pipes, hot water storage tanks or refrigerators, and as a trim piece in automobile manufacturing. Has. Polyurethane is especially used in automobile manufacturing, for example in automotive exterior trims such as spoilers, roof members, suspension members and in automotive interior trims such as headliners, foam carpet backings, door trims, steering wheels, gear knobs and seat cushions. Often used.

Polyurethane is known to have an unpleasant odor or a tendency to emit organic substances that may cause discomfort in the case of high concentration. Closed spaces, for example interiors of buildings or vehicles, for example automobiles, are particularly affected. One example of this release is the release of aldehydes. Various approaches already exist to reduce aldehyde emissions.

Thus, for example, EP 1428847 describes that aldehyde emissions can be reduced by subsequent addition of a polymeric material having primary and/or secondary amino groups. The amine groups in the polymer are responsible for reducing the amount of emission. Polymeric active materials have to be applied to previously produced foams as they are isocyanate reactive and are very largely deactivated by reaction with isocyanates. The downside here is the cumbersome process involving the additional step of post-treatment of the foam. It cannot be used in compact systems or closed cell foams.

US 20130203880 describes the use of polyhydrazodicarbonamides as substances to reduce aldehyde emissions in polyurethane foams. However, a significant reduction in aldehyde is achieved only when a large amount of polyhydrazodicarbonamide of 2% to 5.5% by weight is added to the polyol component. Since polyhydrazodicarbonamide likewise has catalytic properties, the addition of this material at this scale changes the reaction profile. Moreover, the aldehyde reduction achieved requires further improvement even when large amounts of polyhydrazodicarbonamide are used.

US 2006/0141236 describes the use of hydrazine compounds in polyurethanes as aldehyde scavengers. The active substance is added directly to the polyol component. The examples illustrate the use of acethydrazide, carbohydrazide and adipic dihydrazide. This can reduce aldehyde emissions by 60% to 70%.

WO 2015082316 describes the use of a CH-acidic compound of the general formula R ¹ -CH ₂ -R ² , wherein R ¹ and R ² are independently of each other to attract electrons to reduce formaldehyde emission in combination with an incorporable catalyst Represents a radical. This can effectively reduce formaldehyde, but the foam specimens still show high emissions of volatile organics, leading to high TVOC values according to VDA 277.

WO 2016188675 describes the use of a compound obtainable by esterification of a CH-acidic substance, for example polyetherol and methyl acetoacetate. Here too, the release of formaldehyde can be effectively reduced, but the high release of other organic compounds (e.g. high TVOC values according to VDA 277) is maintained at relatively high temperatures, especially as achieved for example in the production of foams. .

WO 2017207687 describes the use of malon hydrazide to reduce the emission of organic substances. The disadvantage of these materials is that they are poorly soluble and cannot be completely soluble in the commonly used polyol components, and the cost of these compounds is high.

It was an object of the present invention to provide a polyurethane, in particular polyurethane foam, which exhibits a reduced release of organic substances such as aldehydes, in particular formaldehyde and acetaldehyde. In particular, the substances responsible for the reduction in aldehyde emissions should have a long lasting effect and should not lead to further release of the polyurethane. In addition, the low-emission polyurethane foam should be able to be produced by a simple process that allows the addition of substances that reduce the amount of aldehyde emission directly to the reaction mixture for polyurethane production. In particular, inexpensive and easy-to-handle materials that do not interfere with polyurethane production should be used.

The object of the present invention is (a) a polyisocyanate, (b) a polymer compound having an isocyanate-reactive group, (c) a catalyst, and optionally (d) a blowing agent, (e) a chain extender and/or a crosslinking agent and (f) an auxiliary agent and/or Or mixing an additive to provide a reaction mixture and reacting the reaction mixture to provide polyurethane, wherein the polymer compound (b) is obtained by polycondensation of an acid component and an alcohol component. Can be polyesterol (b1), the acid component comprises malonic acid and/or derivatives thereof, and the alcohol component comprises an aliphatic dialcohol having 4 to 12 carbon atoms. . In addition, the object of the invention is achieved by the polyurethane obtainable by the process according to the invention. The invention further provides for the use of the polyurethane according to the invention in enclosed spaces, for example vehicles.

"Polyurethane" in the context of the present invention includes all known polyisocyanate polyaddition products. These include adducts of isocyanates and alcohols, and modified polyurethanes that may include isocyanurate, allophanate, urea, carbodiimide, uretonimine and biuret structures and additional isocyanate adduct products. Such polyurethanes according to the invention are in particular solid polyisocyanate polyaddition products such as duromers, and foams based on polyisocyanate-polyaddition products such as flexible foams, semi-rigid foams, rigid foams or integral foams, and also polyurethane coatings. And a binder. "Polyurethane" should be further understood to mean a polymer blend comprising polyurethane and additional polymers, and also foams made from such polymer blends. The polyurethane according to the invention is preferably a polyurethane foam or solid polyurethane which does not contain additional polymers in addition to the polyurethane units (a) to (f) described below.

"Polyurethane foam" in the context of the invention should be understood to mean a foam according to DIN 7726. The flexible polyurethane foam according to the invention has a compressive stress of 15 kPa or less, preferably 1 to 14 kPa and in particular 4 to 14 kPa at 10% compressive/compressive strength according to DIN 53 421/DIN EN ISO 604. The semi-rigid polyurethane foam according to the invention has a compressive stress of greater than 15 and less than 80 kPa at 10% compression according to DIN 53 421/DIN EN ISO 604. According to DIN ISO 4590 the semi-rigid polyurethane foams and flexible polyurethane foams according to the invention preferably have an open cell content of more than 85%, particularly preferably of more than 90%. Further details of the flexible polyurethane foam and semi-rigid polyurethane foam according to the present invention can be found in ["Kunststoffhandbuch", Volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 5].

The rigid polyurethane foam according to the invention exhibits a compressive stress of at least 80 kPa, preferably at least 120 kPa, particularly preferably at least 150 kPa at 10% compression. In addition, rigid polyurethane foams have a closed cell content of more than 80%, preferably more than 90% according to DIN ISO 4590. Further details on the rigid polyurethane foam according to the present invention can be found in ["Kunststoffhandbuch", Volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 6].

"Elastic polyurethane foam" in the context of the present invention should be understood to mean a polyurethane foam according to DIN 7726, which after a simple deformation of 50% of the thickness according to DIN 53 577, after 10 minutes of 2% of the starting thickness. It does not show excessive sustained deformation. Rigid polyurethane foams, semi-rigid polyurethane foams or soft polyurethane foams may be involved.

"Integral polyurethane foam" should be understood to mean a polyurethane foam according to DIN 7726 having an edge zone with a higher density than the core as a result of the molding process. The overall apparent density averaged over the core and edge regions is preferably greater than 100 g/L. The integral polyurethane foam in the context of the present invention can also be a rigid polyurethane foam, a semi-rigid polyurethane foam or a soft polyurethane foam. Further details on the integral polyurethane foam according to the present invention can be found in ["Kunststoffhandbuch", Volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 7].

The polyurethane according to the present invention comprises a polyisocyanate (a), a polymer compound having an isocyanate-reactive group (b), a catalyst (c), and optionally a blowing agent (d), a chain extender and/or a crosslinking agent (f) and an auxiliary agent and/or It is obtained by mixing the additive (f) to give a reaction mixture and reacting the reaction mixture to give a polyurethane, wherein the polymer compound (b) is a polycondensation obtainable by polycondensation of an acid component and an alcohol component. Esterol (b1), the acid component comprises malonic acid and/or derivatives thereof, and the alcohol component comprises aliphatic dialls having 4 to 12 carbon atoms.

In a preferred embodiment, the polyurethane according to the invention is a polyurethane foam with an average density of 10 to 850 g/L, preferably a semi-rigid polyurethane foam or a flexible polyurethane foam or a rigid polyurethane foam, particularly preferably It is an elastic soft polyurethane foam, a semi-rigid polyurethane foam, or an elastic integral polyurethane foam. The elastic integral polyurethane foam preferably has a density averaged over the core and edge regions of 150 g/L to 500 g/L. The flexible polyurethane foam preferably has an average density of 10 to 100 g/L. The semi-rigid polyurethane foam preferably has an average density of 70 to 180 g/L.

In a further preferred embodiment, the polyurethane is a solid having a density of preferably greater than 850 g/L, preferably 900 g/L to 1400 g/L, particularly preferably 1000 g/L to 1300 g/L. It is polyurethane. A solid polyurethane is obtained without the addition of a blowing agent. The small amount of blowing agent present in the polyol as a result of production, such as water, is not understood in the present invention as constituting the blowing agent addition. The reaction mixture for producing the compact polyurethane preferably comprises less than 0.2% by weight, particularly preferably less than 0.1% by weight and in particular less than 0.05% by weight of water.

The polyurethanes according to the invention are preferably used in the interior of vehicles, such as ships, airplanes, trucks, cars or buses, particularly preferably passenger cars or buses, in particular passenger cars. Hereinafter, interiors of passenger cars and buses are referred to as automobile interior parts. Soft polyurethane foam is used as a seat cushion, semi-rigid polyurethane foam is used as a door trim member or rear foam of an instrument panel, an integral polyurethane foam is used as a steering wheel, shift knob or headrest, and solid polyurethane is used as a cable sheath, etc. I can.

The polyisocyanates (a) used in the production of the polyurethanes according to the invention include all polyisocyanates known for the production of polyurethanes. These include aliphatic, cycloaliphatic and aromatic divalent or polyvalent isocyanates known from the prior art and any desired mixtures thereof. Examples are 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate, higher nuclear homologues of monomeric diphenylmethane diisocyanate and diphenylmethane diisocyanate (polymer MDI), isophorone diisocyanate (IPDI) or a mixture of oligomers thereof, 2,4- or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, tetramethylene diisocyanate or oligomers thereof, hexamethylene diisocyanate (HDI) or oligomers thereof, naphthylene Diisocyanate (NDI) or mixtures thereof.

2,4- and/or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, higher nuclear homologues of monomeric diphenylmethane diisocyanate and/or diphenylmethane diisocyanate (polymer MDI) and mixtures thereof desirable. Additional possible isocyanates are mentioned for example in ["Kunststoffhandbuch", Volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapters 3.2 and 3.3.2].

Polyisocyanate (a) can be used in the form of a polyisocyanate prepolymer. Such polyisocyanate prepolymers contain an excess of the above-described polyisocyanate (component (a-1)) at a temperature of, for example, 20° C. to 100° C., preferably about 80° C., a polymer compound (b) having isocyanate-reactive groups It can be obtained by reacting with (component (a-2)) and/or chain extender (c) (component (a-3)) to provide an isocyanate prepolymer.

The polymer compound (a-2) and the chain extender (a3) having an isocyanate-reactive group are known to those skilled in the art, for example ["Kunststoffhandbuch [Plastics Handbook], volume　7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1]. Thus, for example, what can be used also as the polymer compound (a-2) having an isocyanate-reactive group is a polymer compound having an isocyanate-reactive group described in (b) below. In a preferred embodiment, the polymer compound having an isocyanate-reactive group used as component (a2) comprises polyesterol (b1), and it is also possible to produce a prepolymer using the total amount of polyesterol (b1). When the isocyanate prepolymer is used as the isocyanate (a) it is preferably more than 5% by weight, more preferably 10 to 50% by weight, even more preferably 15 to 40% by weight, particularly preferably 17 to 35% by weight. %, in particular 20 to 30% by weight of an isocyanate content (NCO content).

Usable polymeric compounds (b) having isocyanate-reactive groups include all known compounds having at least two isocyanate-reactive hydrogen atoms, for example those having a functionality of 1 to 8 and a number average molecular weight of 400 to 15,000 g/mol, , Wherein the average functional value averaged for all polymer compounds having isocyanate-reactive groups is at least 2. Thus, it is possible to use, for example, a compound selected from the group of polyether polyols, polyester polyols, also referred to as polyether polyols or polyether alcohols or polyester polyols or polyester alcohols, or mixtures thereof.

Polyether alcohols are, for example, from epoxides such as propylene oxide and/or ethylene oxide, or as aliphatic alcohols, phenols, amines, carboxylic acids, water or natural based compounds such as suc, active hydrogens such as sorbitol or mannitol. It is produced using a catalyst from tetrahydrofuran with a starting compound. Suitable catalysts here include, for example, basic catalysts or double metal cyanide catalysts as described in PCT/EP2005/010124, EP 90444 or WO 05/090440.

Polyesterols are, for example, acid components and polyhydric alcohols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and/or containing aliphatic or aromatic dicarboxylic acids or derivatives thereof, preferably in the presence of an esterification catalyst. It can be produced from alcoholic components including hydroxyl-containing aliphatic polycarbonates.

Other possible polyols are listed for example in ["Kunststoffhandbuch, Band 7, Polyurethane" [Plastics Handbook, volume 7, Polyurethanes], Carl Hanser Verlag, 3rd edition 1993, chapter 3.1].

Also usable in addition to the described polyetherols and polyesterols are filler-containing polyetherols and polyesterols, also known as polymer polyetherols or polymer polyesterols. Such compounds preferably comprise dispersed particles of a thermoplastic plastic composed of olefin monomers, for example acrylonitrile, styrene, (meth)acrylate, (meth)acrylic acid and/or acrylamide. Polyols containing such fillers are known and commercially available. Their production is described, for example, in DE 111 394, US 3 304 273, US 3 383 351, US 3 523 093, DE 1 152 536, DE 1 152 537 WO 2008/055952 and WO2009/128279.

The polymeric compound (b) according to the invention having an isocyanate-reactive group further comprises at least one polyesterol (b1) obtainable by polycondensation of an acid component and an alcohol component, wherein the acid component is malonic acid and/or Derivatives thereof, and the alcohol component includes aliphatic dialcohols having 4 to 12 carbon atoms.

The acid component includes malonic acid or a derivative thereof. "Acid derivative" in the context of the present invention is to be understood as meaning any derivative of an acid that can react with an alcohol to give an ester. Such derivatives include, for example, acid chlorides, acid anhydrides or esters such as methyl or ethyl esters. In addition to malonic acid or derivatives thereof, the acid component may comprise one or more further di- or polycarboxylic acids or derivatives thereof, preferably diacids having 2 to 12, preferably 6 to 12 carbon atoms. . Preferred examples are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. When the acid component further comprises di- or polycarboxylic acids or derivatives thereof in addition to malonic acid or derivatives thereof, they particularly preferably comprise aliphatic diacids or derivatives thereof, in particular adipic acid. In a particularly preferred embodiment, only malonic acid and adipic acid, in each case optionally also derivative forms thereof, are used as acid components.

The acid component preferably comprises 20 to 100 mol%, more preferably 60 to 100 mol%, in particular 80 to 100 mol% of malonic acid or derivatives thereof.

The alcohol component comprises aliphatic dialcohols having 4 to 12 carbon atoms, such as butanediol, pentanediol, hexanediol or decanediol, preferably pentanediol and/or hexanediol, in particular hexanediol. In addition to these alcohols, additional mono-, di- or polyalcohols may also be present in the alcohol component, for example those having a molecular weight of 62 to 400 g/mol. Examples are monoethylene glycol, 1,2- or 1,3-propanediol, diethylene glycol, dipropylene glycol, glycerol, pentaerythritol or trimethylolpropane.

These dialcols having 4 to 12 carbon atoms preferably have terminal OH groups. It is particularly preferred when the alcohol component comprises 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or 1,10-decanediol, especially 1,6-hexanediol. The proportion of dialcohols having 4 to 12 carbon atoms, based on the alcohol component, is preferably 50 to 100 mol%, particularly preferably 70 to 100 mol%, in particular 80 to 98 mol%. A particularly preferred embodiment is 2 using a dialcohol having 4 to 12 carbon atoms as well as an alcohol having a functionality of 3 or more, for example a trialcohol such as glycerol or trimethylolpropane, or a quatrol such as pentaerythritol. The functionality of the excess polyether (b1) is established.

The polyester alcohol (b1) is preferably 10 to 300, particularly preferably 15 to 250, more preferably 20 to 200, even more preferably 30 to 150, even more preferably 40 to 100, particularly 50 It has a hydroxyl number of to 80. The number average molecular weight of the polyester alcohol (b1) is preferably more than 750 g/mol, more preferably 850 to 5000 g/mol, particularly preferably 1000 to 3000 g/mol, in particular 1000 to 2500 g/mol to be.

The average functionality of the polyesterol (b1) is preferably 1 to 8, more preferably 2 to 6, particularly preferably 2 to 4, more preferably 2 to 3, even more preferably 2.1 to 2.8, Especially 2.3 to 2.7. Effect adjustment is known. Thus, the functionality can be adjusted through the proportion of the acid having a functionality greater than 2 in the acid component and the proportion of the alcohol having functionality greater than 2 in the alcohol component.

The weight ratio of polyesterol (b1) based on the total weight of the polymer compound (b) having an isocyanate-reactive group is preferably 0.1 to 50% by weight, particularly preferably 1 to 30% by weight, more preferably 2 to 25% by weight, even more preferably 3 to 20% by weight, even more preferably 4 to 15% by weight, in particular 5 to 10% by weight. In a particularly preferred embodiment of the invention, component (b) comprises polyetherol, and in a further preferred embodiment, in addition to polyesterol (b1) no further polyesterols.

In a particularly preferred embodiment, the content of malonic acid radicals of the formula -OC(O)-CH ₂ -C(O)-O-, based on the total weight of the polymer compound (b) having an isocyanate reactive group, is 0.01 to 30% by weight , More preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, in particular 1 to 10% by weight.

The catalyst (c) greatly accelerates the reaction of the polyol (b) and optionally chain extenders and crosslinkers (e) and chemical blowing agents (d), and organic, optionally modified polyisocyanates (a). The catalyst (c) preferably comprises an incorporable amine catalyst.

Typical catalysts that can be used in the production of polyurethanes are, for example, amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, Dimethylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine , N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole , 1-azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N- Ethyl diethanolamine, and dimethylethanolamine. Likewise organometallic compounds, preferably organotin compounds, such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) Laurate and dialkyltin (IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylate, e.g. For example bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof are contemplated. The organometallic compound may be used alone or preferably in combination with a strong basic amine. When component (b) is an ester, it is preferred to use only an amine catalyst.

The incorporable amine catalyst is at least one reactive toward an isocyanate such as a primary amine group, a secondary amine group, a hydroxyl group, an amide or urea group, preferably a primary amine group, a secondary amine group, a hydroxyl group, It preferably has 1 to 8, particularly preferably 1 to 2 groups. Incorporable amine catalysts are mainly used in the production of low-emission polyurethanes, which are particularly used in automotive interiors. Such catalysts are known and are described for example in EP1888664. These include compounds which, in addition to the isocyanate reactive group(s), preferably contain at least one tertiary amino group. At least one tertiary amino group in the incorporable catalyst contains preferably at least two aliphatic hydrocarbon radicals having preferably 1 to 10 carbon atoms per radical, particularly preferably 1 to 6 carbon atoms per radical. Retain. It is particularly preferred when the tertiary amino group carries two radicals independently selected from methyl and ethyl radicals and a further organic radical. Examples of incorporable catalysts that can be used are bis(dimethylaminopropyl)urea, bis(N,N-dimethylaminoethoxyethyl) carbamate, dimethylaminopropylurea, N,N,N-trimethyl-N-hydroxyethyl Bis(aminopropyl ether), N,N,N-trimethyl-N-hydroxyethylbis(aminoethyl ether), diethylethanolamine, bis(N,N-dimethyl-3-aminopropyl)amine, dimethylaminopropyl Amine, 3-dimethylaminopropyl-N,N-dimethylpropane-1,3-diamine, dimethyl-2-(2-aminoethoxyethanol), (1,3-bis(dimethylamino)propan-2-ol) , N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, bis(dimethylaminopropyl)-2-hydroxyethylamine, N,N,N-trimethyl-N-(3-aminopropyl)- Bis(aminoethylether), 1,4-diazabicyclo[2.2.2]octane-2-methanol and 3-dimethylaminoisopropyl diisopropanolamine or mixtures thereof.

The catalyst (c) can be used as a catalyst/catalyst combination, based on the weight of component (b), in a concentration of, for example, 0.001 to 5% by weight, in particular 0.05 to 2% by weight. In a particularly preferred embodiment, an exclusively incorporable catalyst is used as catalyst (c).

When the polyurethane according to the invention is in the form of a polyurethane foam, the reaction mixture according to the invention further comprises a blowing agent (d). Any blowing agent known for polyurethane production can be used. These may include chemical and/or physical blowing agents. Such blowing agents are described for example in ["Kunststoffhandbuch [Plastics Handbook], volume 　7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter 　3.4.5]. "Chemical blowing agent" is understood to mean a compound that forms a gaseous product by reaction with an isocyanate. Examples of such blowing agents are water or carboxylic acids. "Physical blowing agent" is understood to mean a compound that is dissolved or emulsified in the input material of polyurethane production and vaporized under the conditions of polyurethane formation. Examples include hydrocarbons, halogenated hydrocarbons and other compounds such as perfluorinated alkanes such as perfluorohexane, chlorofluorohydrocarbons and ethers, esters, ketones, acetals and/or liquid carbon dioxide. The blowing agent can be used in any desired amount. The blowing agent is preferably used in an amount in which the resulting polyurethane foam has a density of 10 to 850 g/L, particularly preferably 20 to 800 g/L, in particular 25 to 500 g/L. It is particularly preferred to use a blowing agent comprising water.

Chain extenders and crosslinkers (e) that can be used include compounds having at least two isocyanate-reactive groups and having a molecular weight of less than 400 g/mol, wherein molecules having two isocyanate-reactive hydrogen atoms are referred to as chain extenders and have 2 Molecules with more than four isocyanate reactive hydrogens are referred to as crosslinkers. However, it is also possible to omit the chain extender or crosslinking agent. However, the addition of chain extenders, crosslinking agents or optionally mixtures thereof may be advantageous for modifying mechanical properties, such as hardness.

When chain extenders and/or crosslinkers are used they are in each case from 0.5 to 60% by weight, preferably from 1 to 40% by weight, especially preferably from 1.5 to 60% by weight, based on the total weight of components (b) to (e). It is usually used in an amount of 20% by weight.

Where chain extenders and/or crosslinkers (e) are used, chain extenders and/or crosslinkers familiar to polyurethane production may be used. These are preferably low molecular weight compounds with isocyanate-reactive functional groups, for example glycerol, trimethylolpropane, glycols and diamines. Further possible low molecular weight chain extenders and/or crosslinkers are mentioned for example in ["Kunststoffhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapters 3.2 and 3.3.2].

Auxiliaries and/or additives (f) may also be used. All auxiliaries and additives known for polyurethane production can be used. Examples include surface active substances, foam stabilizers, cell modifiers, release agents, fillers, dyes, pigments, flame retardants, hydrolysis stabilizers, fungicides and bacteriostatic substances, and also antioxidants. Such materials are known and are described for example in ["Kunststoffhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapters 3.4.4 and 3.4.6 to 3.4.11].

In particular, the combination of polyesterol (b1) and antioxidant further reduces the release of organic substances such as aldehydes. Examples of antioxidants are phenolic substances such as 2,6-di-tert-butyl-4-methylphenol, benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 Branched alkyl esters, amine-based antioxidants such as N,N'-di-isopropyl-p-phenylenediamine, thiosynergists such as dilauryl 5-thiodipropionate, phosphites and phosphonites such as Triphenylphosphite, diphenylalkylphosphite, benzofuranone and indolinone, other antioxidants such as O-, N- and S-benzyl compounds, triazine compounds, β-(3,5-di-tert-butyl Amides of -4-hydroxyphenyl)propionic acid, esters of substituted and unsubstituted benzoic acid, esters of nickel compounds and β-10-thiodipropionic acid, or mixtures of two or more of these antioxidants. Such antioxidants are described for example in WO2017125291 and are commercially available, for example under the trade names Irganox 1076, Irganox 245, Irganox 2000, Irganox E201 (vitamin E), Irganox 5057 or Irgafos 38.

The preparation of the polyurethanes according to the invention generally comprises (a) a polyisocyanate, (b) a polymer compound having an isocyanate-reactive group, (c) a catalyst, and optionally (d) a blowing agent, (e) a chain extender and/or a crosslinking agent, and (f) mixing auxiliaries and/or additives to provide a reaction mixture and reacting the reaction mixture to provide polyurethane. Components (a) to (c), and optionally (d) to (f), for the sum of the reactive hydrogen atoms of components (b), (c), (d), and optionally (e) and (f) The reaction is carried out in an amount such that the equivalent ratio of the NCO groups of the polyisocyanate (a) is 0.75 to 1.5:1, preferably 0.8 to 1.25:1. When the cellular plastic at least partially comprises an isocyanurate group, the polyisocyanate (a) to the sum of the reactive hydrogen atoms of components (b), (c), (d), and optionally (e) and (f) A ratio of NCO groups of 1.5 to 20:1, preferably 1.5 to 8:1 is generally used. A ratio of 1:1 corresponds to an isocyanate index of 100.

A two-component process of mixing and reacting the polyol component (A) and the isocyanate component (B) is often used. The isocyanate component (B) and the polyol component (A) are each mixed in advance. The isocyanate component (B) comprises a polyisocyanate (a) and the polyol component (A) is usually a polymer compound (b) having an isocyanate-reactive group, a catalyst (c), and optionally a blowing agent (d), a chain extender and/or a crosslinking agent. (e) and adjuvants and/or additives (f). When the prepolymer is used as the isocyanate component (B), a part of the isocyanate-reactive component selected from, for example, a polymer compound (b) having an isocyanate-reactive group and/or a chain extender and/or a crosslinking agent (e) is also a compound ( It can be mixed with a-1) to give a polyisocyanate polymer. Such polyisocyanate prepolymers are described in polyisocyanate (a). In one embodiment of the present invention, polyesterol (b1) is used to prepare isocyanate component (B) such that polyol component (A) does not contain polyesterol (b1). In a further embodiment of the invention, the polyester alcohol (b1) is partly or preferably completely included in the polyol component (A).

The specific starting materials (a) to (f) for producing the polyurethane according to the present invention are, in each case, the polyurethane of the present invention to be produced is a thermoplastic polyurethane, a flexible foam, a semi-rigid foam, a rigid foam or an integral foam. There is only a slight difference both quantitatively and qualitatively. Thus, for example, the production of solid polyurethanes does not use blowing agents and the production of thermoplastic polyurethanes mainly uses strictly bifunctional starting materials. Further, the elasticity and hardness of the polyurethane according to the present invention can be varied through the chain length and the functionality of, for example, a high molecular weight compound having two or more reactive hydrogen atoms. Such modifications are known to those skilled in the art.

The reactants for producing solid polyurethanes are described for example in EP 0989146 or EP 1460094, the reactants for producing flexible foams are described for example in PCT/EP2005/010124 and EP 1529792, semi-rigid foams The reactants for producing the are described for example in ["Kunststoffhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 5.4], and the reactants for producing the rigid foam are for example PCT/EP2005/ 010955, thermoplastic moldable rigid foams are described, for example, in EP 2247636, and reactants for producing an integral foam are described, for example, in EP 364854, US 5506275 or EP 897402. Some of the polyols described in this document are replaced by polyesterol (b1).

In addition to the process according to the invention, the invention further provides a polyurethane obtainable by the process according to the invention.

The release of organic substances from the polyurethane can also be caused by contact of the polyurethane reacting or reacting with the polyesterol (b1). Polyurethane can be produced in any desired manner and need not be produced using polyesterol (b1). This production is known to the person skilled in the art and is described in the cited literature. The polyurethane thus produced is then wetted with polyesterol (b1), for example by spray application of polyesterol itself or a solution comprising polyesterol (b1), for example an aqueous solution. Polyesterol (b1) can also be used as part of a release agent and can be applied directly to the resulting polyurethane after mold coating. The amount of polyesterol (b1) to be applied in each case is generally 0.1 to 20% by weight, particularly preferably 1 to 15% by weight, more preferably based on the total weight of the polyurethane without polyesterol (b1). It is preferably 1.5 to 10% by weight, even more preferably 2 to 6% by weight. The present invention further provides such polyurethanes.

The polyurethane according to the invention is preferably in closed spaces, for example in residential buildings, as insulation, for example pipes and refrigerators, in furniture structures, for example as decorative elements or seat cushions, mattresses, and vehicles. In interiors, for example in automobile interiors, for example steering wheels, dashboards, door trims, carpet foam backings, acoustic foams such as headliners, and also as headrests or gear knobs. In the case of the polyurethane according to the invention, the release of both formaldehyde and acetaldehyde is significantly reduced not only when compared to a reference product without additives, but also compared to prior art additives for aldehyde reduction. The polyurethanes according to the invention further emit very small amounts of volatile organic compounds (VOC) according to VDA 278 and TVOC according to VDA 277. Compound (b1) is thermally stable. As a result, this compound does not lose activity even at reaction temperatures up to 200°C, which can occur in the production of certain polyurethane foams. Polyester alcohols (b1) are also typically polymeric compounds (b) having isocyanate-reactive groups as well as catalysts (c) and blowing agents, if present, in particular blowing agents comprising water (d), chain extenders and/or crosslinking agents (e ) And in conventional polyol components, which may comprise auxiliaries and/or additives (f). Storage stability in the context of the present invention is that the cream and rise time in a beaker test at room temperature after storage in a sealed container at room temperature is 50% or less, preferably 30%, in particular 20, compared to the mixing time to provide the polyol component. It should be understood to mean changing to %. The storage stability is preferably more than 1 week, particularly preferably more than 4 weeks, especially more than 3 months.

Polyesterol (b1) may additionally be used as an adhesion promoter for improving the adhesion of the polyurethane according to the present invention to plastics. Accordingly, the present invention also relates to a composite member comprising a plastic to which the polyurethane according to the present invention is adhesively bonded, wherein the composite member applies the polyurethane reaction mixture according to the present invention to the plastic and reacts it to It can be obtained by providing urethane.

The composite member according to the present invention comprising the polyurethane and plastic according to the present invention may comprise, for example, a thermosetting plastic or a thermoplastic plastic as plastic. It is preferred to use a thermoplastic plastic. Typical thermoplastic plastics include, for example, polyphenylene oxide (PPO), polyvinyl chloride (PVC), acrylonitrile butadiene styrene (ABS), polymethyl methacrylate (PMMA), acrylonitrile styrene acrylic ester (ASA). ), polycarbonate (PC), thermoplastic polyurethane (TPU), polyethylene (PE), polypropylene (PP). The composite member is preferably a plastic (i) as a thermoplastic polyolefin (TPO), such as polyethylene and/or polypropylene, polyvinyl chloride (PVC), styrene maleic anhydride (SMA) and/or polycarbonate/styrene-acrylonitrile. /Acrylonitrile-butadiene blends (PC/ABS), preferably in the form of films, sheets or as cable materials.

Plastics (i) can be used in the form of conventional materials for the production of composite members, such as sheets or films, generally 0.2 to 2 mm thick.

Such films are commercially available and their preparation is well known. The film preferably has a thickness of 0.2 to 2 mm. Also, what can be used as (i) is a film comprising at least two layers, for example one layer comprising an ASA and/or polycarbonate material.

Plastics further include all conventional plastic-based materials commonly used for insulation of electrical conductors. These include polyvinyl chloride (PVC), thermoplastic polyurethane (TPU), polypropylene (PP) and ethylene tetrafluoroethylene (ETFE).

Plastics composed of styrene maleic anhydride (SMA) and/or a polycarbonate/styrene-acrylonitrile/acrylonitrile-butadiene blend (PC/ABS) can be used as composite parts, for example reinforced parts for instrument panels or door trim parts. It can be used in the form of conventional materials to produce. Skin materials for this application are often made of thermoplastic polyolefin (TPO) and polyvinyl chloride (PVC).

When used as an adhesion promoter, the polyester (b1) has a hydroxyl number of 30 to 100, preferably 40 to 90 and particularly preferably 50 to 75 mg KOH/g. The proportion of the adhesion promoter is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, especially 1 to 5% by weight, based on the total weight of the compound (b) having an isocyanate-reactive group.

The production of the composite member according to the invention is carried out by contacting the reaction mixture for producing the polyurethane according to the invention with plastics, usually without the use of additional adhesion producing materials such as adhesives. The plastics and reaction mixture for preparing the polyurethane according to the invention are preferably brought into contact with each other, for example in a mold. The production of polyurethanes, for example flexible foams, semi-rigid foams or integral foams, particularly preferably semi-rigid foams and integral foams, is otherwise done according to well-known processes, for example one-shot processes, with well-known tools, molds , Mixing device and administration means are used.

The composite member according to the invention exhibits a markedly improved adhesion between plastic and polyurethane, in particular due to the use of polyester polyol (b1). This adhesion can be determined in a number of ways, such as measuring the force required to detach the plastic. In the case of sheet-like bonded composites, the peel force between the plastic and the polyurethane according to DIN 53289 or 53530 of at least 2.5 N/cm is preferably achieved in the new condition and after storage at high and high temperatures/humidity. Adhesion can also be determined according to subjective evaluation criteria. The longitudinal watertightness in the cable sheath and grommets is guaranteed only when there is an adhesive force between the plastic and polyurethane. It is tested according to, for example, DELPHI's internal specifications (REI-WDP 1), Ford's internal specifications (WSS-M15P45-A: FLTM-BI 104-01) or the standard of PSA-Peugeot-Citroen (B21 7050). The sample fails (F) if the receiving tube is placed on one side of the grommet and the moisture can be measured on the other side of the grommet. The permeability of the cable sheath is sometimes further evaluated by performing tests with elevated air pressure and measuring the pressure drop.

The composite member according to the invention is preferably used as a component of vehicle or aircraft manufacturing or building structures, for example as dashboards, door trims, vehicle trunk shelves, consoles, armrests or door mirrors. The composite member according to the invention is additionally used as an outer sheath of an electrical conductor. This includes not only the production of dimensionally stable foam cable sets, but also the production of grommets, connectors and relay potting. Polyurethane is preferably in the foamed form for products in vehicle or aircraft manufacturing and in the insulation of building structures and electrical conductors. In the case of connector and relay potting, the polyurethane is preferably of compact form.

The invention will be described below with reference to examples.

Starting material:

Polyol A: glycerol-starting polyether based on ethylene oxide and propylene oxide with an average OH of 28 mg KOH/g, a functionality of 2.7, and a propylene oxide content of 84% by weight based on the total weight of the polyether Polyol.

Polyol B: A polyether polyol with an OH of 250 mg KOH/g and a functionality of 2.0, based on polyol A (35% by weight), propylene oxide (45% by weight) and dimethylaminopropylamine (20% by weight).

Polyol C: based on sucrose, glycerol and propylene oxide, i.e. sucrose content 20% by weight, glycerol content 13% by weight and propylene oxide content 67% by weight, having an OH of 490 mg KOH/g and a functionality of 4.3 Polyetherol.

Isocyanate A: A mixture having an NCO content of 29.8% by weight of 85% by weight of carbodiimide-modified 4,4'-MDI and 15% by weight of polymeric diphenylmethane diisocyanate (PMDI).

TEOA: Triethanolamine

Isopur SU-12021: ISL-Chemie's Black Color Paste

Jeffcat DPA: Huntsman's Catalyst

Jeffcat ZF10: Huntsman's Catalyst

additive:

V1: trimethylolpropane triacetoacetate

V2: reaction product of malonic acid and diethylene glycol (2:3, Mw 458 g/mol)

V3: esterification product of 1 mol of polyol C and 4 mol of methyl acetoacetate

V4: Polyester polyol consisting of adipic acid, 1,4-butanediol, isophthalic acid, monoethylene glycol, having an average OH number of 55 mg KOH/g.

A1: Polyester polyol consisting of diethyl malonate, adipic acid (molar ratio 4:1), 1,6-hexanediol and glycerol, having an average OH number of 70 mg KOH/g.

A2: Polyester polyol consisting of diethyl malonate, 1,6-hexanediol and glycerol, with an average OH number of 71 mg KOH/g.

A3: Polyester polyol consisting of diethyl malonate, adipic acid (molar ratio 4:1) and 1,6-hexanediol, having an average OH number of 58 mg KOH/g.

A4: Polyester polyol consisting of diethyl malonate and 1,6-hexanediol with an average OH number of 56 mg KOH/g.

Synthesis of Additives A1 to A4

Synthesis of A1:

142.29 g of adipic acid, 0.01 g of TTB (titanium (IV) butoxide CAS: 5593-70-4), 23.02 g of glycerol and 604.87 g of 1,6-hexanediol, thermometer, nitrogen inlet, heating mantle , Initially put into a 4 l round neck flask equipped with a distillation column and a stirrer and heated to 120°C. Once the acid was completely dissolved, the temperature was increased stepwise to 240° C. and the water was distilled at 240° C. over several hours. After 4 hours, the acid value was 0.1 mg KOH/g and the reaction mixture was cooled to 150°C. 623.79 g of diethyl malonate was added and the reaction temperature was increased stepwise to 180°C. After 8 hours, an additional 19 g of diethyl malonate was added and the batch was stirred at 180° C. for an additional 6 hours. An additional 6.9 g of diethyl malonate was added and ethanol was distilled at 180° C. for an additional 2 hours. The batch was cooled and stabilized with 1.5 g of Irganox 1076. A colorless polyester polyol having a hydroxyl value of 70.3 mg KOH/g, an acid value <0.1 mg KOH/g and a viscosity of 5118 mPas at 25°C was obtained.

Synthesis of A2:

855.74 g of diethyl malonate, 630.87 g of 1,6-hexanediol, 23.02 g of glycerol and 0.01 g of TTB (titanium (IV) butoxide CAS: 5593-70-4), thermometer, nitrogen inlet, heating It was initially introduced into a 4 L round neck flask equipped with a mantle, a distillation column and a stirrer. The temperature was increased stepwise to 160°C. Ethanol was distilled at 160° C. for 7 hours. Then an additional 50 g of diethyl malonate was added and the reaction mixture was boiled at 160° C. for 7 hours. The product was stabilized with 1.5 g of Irganox 1076. A colorless polyester polyol having a hydroxyl value of 71 mg KOH/g, an acid value <0.1 mg KOH/g, and a viscosity of 3114 mPas at 25°C was obtained.

Synthesis of A3:

141.31 g of adipic acid, 0.01 g of TTB (titanium (IV) butoxide CAS: 5593-70-4) and 630.45 g of 1,6-hexanediol were mixed with a thermometer, nitrogen inlet, heating mantle, distillation column and stirrer. It was initially put into a mounted 4 L round neck flask and heated to 120°C. Once the acid was completely dissolved, the temperature was increased stepwise to 240° C. and the water was distilled at 240° C. over several hours. After 5 hours, the acid value was 0.1 mg KOH/g and the reaction mixture was cooled to 150°C. 619.50 g of diethyl malonate was added and the reaction temperature was increased stepwise to 180°C. After 11 hours, an additional 16.5 g of diethyl malonate was added and the batch was stirred at 180° C. for an additional 3 hours. The batch was cooled and stabilized with 1.50 g of Irganox 1076. A colorless polyester polyol having a hydroxyl value of 57.7 mg KOH/g, an acid value <0.1 mg KOH/g and a viscosity of 4698 mPas at 25°C was obtained.

Synthesis of A4:

809.37 g of diethyl malonate, 656.28 g of 1,6-hexanediol and 0.01 g of TTB (titanium (IV) butoxide CAS: 5593-70-4), thermometer, nitrogen inlet, heating mantle, distillation column and stirrer Was initially added to a 4 l round neck flask equipped with. The temperature was increased stepwise to 160°C. Ethanol was distilled at 160° C. for 4 hours. Then an additional 50 g of diethyl malonate was added and the reaction mixture was boiled at 160° C. for 5 hours. The product was stabilized with 1.5 g of Irganox 1076. A colorless polyester polyol having a hydroxyl value of 56.1 mg KOH/g, an acid value <0.1 mg KOH/g and a viscosity of 3338 mPas at 25°C was obtained.

Way:

Viscosity measurement: Unless otherwise specified, the viscosity of polyols is measured in DIN EN ISO with a Rheotec RC 20 rotary viscometer using a CC 25 DIN spindle (spindle diameter: 12.5 mm; cylinder bore measurement: 13.56 mm) at a shear rate of 50 1/s. Measured at 25° C. according to 3219 (1994).

Determination of hydroxyl number: The hydroxyl number was determined by the phthalic anhydride method DIN 53240 (1971-12) and reported in mg KOH/g.

Measurement of acid value: The acid value was determined according to DIN EN 1241 ( 1998-05 ) and reported in mg KOH/g.

Formaldehyde was measured by a procedure similar to ASTM D-5116-06. The chamber size was 4.7 liters. The polyurethane sample used was a piece of size 110 mm x 100 mm x 25 mm in the foam interior. During the measurement, the temperature of the measurement chamber was 65°C and the relative humidity was 50%. The air exchange rate was 3.0 liters per hour. An exhaust stream comprising volatile aldehydes from the polyurethane was passed over 120 minutes through a cartridge comprising silica coated with 2,4-dinitrophenylhydrazine. The DNPH cartridge was then eluted with a mixture of acetonitrile and water. The formaldehyde concentration in the eluent was measured by HPLC. In this setting, the detection limit of formaldehyde release was ≤ 11 μg/m ³ .

TVOC was determined by a procedure in accordance with VDA 277.

To examine the adhesion, a test specimen was prepared as described above and a PVC film (test film, 0.42 mm, Benecke-Kaliko, Germany) was placed in a mold. Adhesion was evaluated 1 hour after production using a subjective test method. This was done by peeling the PVC film from the polyurethane sheet and evaluating the adhesion using a rating scale from 1 to 5.

Scale definition:

5 Adhesion breakdown, no adhesion

4 Adhesive destruction, PVC film that can be easily removed from the polyurethane sheet

3 Adhesive destruction, PVC film removable from polyurethane sheet

2 Adhesion destruction, PVC film that is difficult to remove from polyurethane sheet

1 Adhesion destruction, PVC film that is very difficult to remove from polyurethane sheet

An evaluation of 1-2 generally corresponds to sufficient adhesion, for example in automotive applications.

General production example

Mixture A was produced by mixing the following ingredients.

87.1 parts by weight of polyol A

3.0 parts by weight of polyol B

1.5 parts by weight of TEOA

0.5 parts by weight of Isopur SU-12021

2.3 parts by weight of water

0.4 parts by weight Jeffcat DPA

0.2 parts by weight Jeffcat ZF10

0.5 or 5 parts by weight of compounds V1-V4 and A1-A4 according to Table 1.

Mixture A and isocyanate A and the additives according to Table 1 were mixed with each other with an isocyanate index of 100 and added to a closed mold to give a molding having an average density of 160 g/L.

characteristic

Table 1 shows the effect of polyesterol (b1) on TVOC, formaldehyde release and also the reaction time after storage according to VDA 277 and also values for adhesion.

Table 1 shows that additives V1 to V3 of the comparative test significantly reduce formaldehyde emissions, while TVOC emissions according to VDA 277 increase significantly compared to the reference (n.m. indicates "not measured"). Compound V4 has excellent adhesion and a low emission amount according to VDA 277, but the formaldehyde emission is within the standard range. In contrast, compounds A1 to A4 of the present invention show a significant reduction in the amount of formaldehyde released as well as the amount released according to VDA 277. These values below 20 ppm are below the maximum values required in the automotive manufacturing sector. Compounds A1 to A4 likewise have essentially no effect on the cream and rise time after storage of mixture A at 50° C. for 1 week, whereas comparative compound V2 results in particularly markedly elevated values. In addition, the example using the polyesterol (b1) of the present invention shows very good adhesion to the PVC film.

Claims (15)

(a) polyisocyanate,
(b) a polymer compound having an isocyanate-reactive group,
(c) a catalyst, and optionally
(d) a blowing agent,
(e) a chain extender and/or crosslinker, and
(f) auxiliaries and/or additives
As a method for producing a polyurethane comprising the step of mixing to provide a reaction mixture and reacting the reaction mixture to provide polyurethane,
Here, the polymer compound (b) is polyesterol (b1) obtainable by polycondensation of an acid component and an alcohol component, the acid component contains malonic acid and/or a derivative thereof, and the alcohol component is 4 to 12 The production method comprising an aliphatic dialcohol having four carbon atoms. The process according to claim 1, wherein in addition to malonic acid and/or derivatives thereof, the acid component comprises at least one further dicarboxylic acid or derivative thereof having 6 to 12 carbon atoms. The method according to claim 1 or 2, wherein the content of malonic acid and/or malonic acid derivative is 20 to 100 mol% based on the total content of the acid component. The production method according to any one of claims 1 to 3, wherein the number average molecular weight of polyesterol (b1) is greater than 750 g/mol. The production method according to any one of claims 1 to 4, wherein the average functional value of polyesterol (b1) is 1 to 8. The production method according to any one of claims 1 to 5, wherein the hydroxyl number of polyesterol (b1) is 10 to 300. The production method according to any one of claims 1 to 6, wherein the weight ratio of polyesterol (b1) is 0.1% to 50% by weight based on the total weight of the polymer compound (b) having an isocyanate-reactive group. The production method according to any one of claims 1 to 7, wherein the polymer compound (b) having an isocyanate-reactive group comprises polyetherol. The process according to any one of claims 1 to 8, wherein the catalyst (c) comprises, in addition to the isocyanate reactive group(s), an incorporable amine catalyst comprising at least one tertiary aliphatic amino group. The method according to any one of claims 1 to 9, wherein the polyurethane is a part of a composite member comprising a plastic to which the polyurethane is adhesively bonded, and the composite member is A method of making that can be obtained by applying a polyurethane reaction mixture to a plastic and reacting it to provide a polyurethane on the plastic. 12. The method of claim 11, wherein the plastic is a thermoplastic plastic. A method for producing a polyurethane comprising contacting the polyurethane with polyesterol (b1). Polyurethane obtainable according to any one of claims 1 to 12. The polyurethane according to claim 13, which is an automobile interior component. Use of the polyurethane according to claim 13 or 14 in the interior of an enclosed space.